Fiber reinforced polyvinyl chloride and copolyester compositions and articles made using these compositions

ABSTRACT

This disclosure pertains to fiber reinforced polyvinyl chloride compositions which comprise fibrous materials, at least one polyvinyl chloride resins and at least one high Tg copolyester. Processes for producing the novel fiber reinforced polyvinyl chloride compositions as well as articles made using these compositions.

FIELD

This disclosure pertains to novel polyvinyl chloride compositions. Moreparticularly, this disclosure pertains to novel compositions containingfibrous materials, polyvinyl chloride resins and copolyesters. Moreparticularly, the present disclosure pertains to fiber-reinforcedpolyvinyl chloride compositions including fibrous materials and highglass transition temperature (Tg) copolyesters to increase the Tg or theheat distortion temperature (HDT) of the polyvinyl chloridecompositions.

BACKGROUND

Fiber-reinforced polyvinyl chloride (PVC) compositions are difficult tomake due to the incompatibility of the fibrous materials such as glassfibers in the PVC matrix and the processing difficulties, such asincreased melt viscosity, that leads to thermal degradation of the PVCduring processing. The compositions of the present disclosure overcomethese processing difficulties and allow for a wider range of processingmethods to be used including calendering, injection molding, and profileand sheet extrusion. Also, historically, commercially available glassfiber filled PVC formulations have been limited to a glass fiber contentof 30% or less. The improved compositions and processing methods in thepresent disclosure allow for fiber content up to 65% thus improving thephysical properties, such as tensile and flexural modulus, of the PVCcompositions.

BRIEF SUMMARY

The fiber reinforced polyvinyl chloride compositions of the presentdisclosure comprise at least one polyvinyl chloride resin, fibrousmaterials and at least one copolyester.

In one embodiment, the fiber reinforced polyvinyl chloride compositionscomprise at least one polyvinyl chloride resin, fibrous materials and atleast one copolyester.

One embodiment of the present disclosure is a polyvinyl chloridecomposition comprising a polyvinyl chloride resin, fibrous materials andat least one copolyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 90 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 10 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 20 to about 60 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms and        -   (ii) about 40 to about 80 mole % of a second modifying            glycol consisting of 2 to 20 carbon atoms,    -   wherein the total mole % of the dicarboxylic acid component is        100 mole %, and wherein the total mole % of the glycol component        is 100 mole %.

One embodiment of the present disclosure is a polyvinyl chloridecomposition comprising a polyvinyl chloride resin, glass fibers and atleast one copolyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 50 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 50 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 60 to about 100 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms; and        -   (ii) about 0 to about 40 mole % of a second modifying glycol            consisting of 2 to 20 carbon atoms;    -   wherein the total mole % of the dicarboxylic acid component is        100 mole %, and wherein the total mole % of the glycol component        is 100 mole %.

In one embodiment, the Tg of the copolyester is at least about 60° C. orhigher.

In one embodiment, the Tg of the copolyester is at least about 90° C. orhigher.

In one embodiment, the Tg of the copolyester is at least about 100° C.or higher.

In one embodiment, the copolyester is amorphous.

In one embodiment, the copolyester has a crystallization half time ofabout 5 minutes or greater.

In one embodiment, the copolyester content in the PVC composition isabout 1 to about 100 parts per hundred resin (phr) based on the contentof the PVC resin in the composition.

In one embodiment, the content of the fibrous materials in the PVCcomposition is up to about 65% by weight based on the total weight ofthe composition.

In another embodiment, the content of the fibrous materials in the PVCcomposition is greater than about 30% by weight based on the totalweight of the composition.

In one embodiment, the polyvinyl chloride compositions are rigid.

One embodiment of the present disclosure is a method of producing afiber reinforced polyvinyl chloride composition comprising:

compounding fibrous materials with a miscible admixture of at least onepolyvinyl chloride resin and at least one copolyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 90 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 10 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 20 to about 60 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms and        -   (ii) about 40 to about 80 mole % of a second modifying            glycol consisting of 2 to 20 carbon atoms,            to produce a viscous thermoplastic material,

extruding the compound through a die to produce pellets; and

introducing the pellets into a calendering, extrusion or injectionmolding process to produce fiber reinforced polyvinyl chloride articles.

One embodiment of the present disclosure is a method of producing afiber reinforced polyvinyl chloride composition comprising:

compounding fibrous materials with at least one copolyester whichcomprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 90 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 10 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 20 to about 60 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms and        -   (ii) about 40 to about 80 mole % of a second modifying            glycol consisting of 2 to 20 carbon atoms,            to produce a viscous thermoplastic material,

mixing the compounded composition with a polyvinyl chloride resin tocreate a polyvinyl chloride composition of about 1 to about 65 percentfibrous materials content based on the total weight of the composition;

extruding the polyvinyl chloride composition through a die to producepellets; and

introducing the pellets into a calendering, extrusion or injectionmolding process to produce fiber reinforced polyvinyl chloride articles.

DETAILED DESCRIPTION

The fiber reinforced polyvinyl chloride compositions of the presentdisclosure comprise at least one polyvinyl chloride resin, fibrousmaterials and at least one copolyester.

In one embodiment, the fiber reinforced polyvinyl chloride compositionscomprise at least one polyvinyl chloride resin, glass fibers and atleast one copolyester.

One embodiment of the present disclosure is a polyvinyl chloridecomposition comprising a polyvinyl chloride resin, fibrous materials andat least one copolyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 90 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 10 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 20 to about 60 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms and        -   (ii) about 40 to about 80 mole % of a second modifying            glycol consisting of 2 to 20 carbon atoms,    -   wherein the total mole % of the dicarboxylic acid component is        100 mole %, and wherein the total mole % of the glycol component        is 100 mole %.

One embodiment of the present disclosure is a polyvinyl chloridecomposition comprising a polyvinyl chloride resin, fibrous materials andat least one copolyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 50 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 50 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 60 to about 100 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms; and        -   (ii) about 0 to about 40 mole % of a second modifying glycol            consisting of 2 to 20 carbon atoms;    -   wherein the total mole % of the dicarboxylic acid component is        100 mole %, and wherein the total mole % of the glycol component        is 100 mole %.        Copolyesters

Any amorphous or essentially amorphous copolyesters are suitable for usein the present disclosure. For example, in one embodiment, anycopolyesters can be used in this disclosure provided that they areessentially amorphous and have a minimum crystallization half-time of atleast about 5 minutes, or at least about 7 minutes. In one embodiment,any copolyester can be used provided that its minimum crystallizationhalf-time is at least about 8 minutes. In another embodiment, anycopolyester can be used provided that its crystallization half-time isat least about 10 minutes. The amorphous copolyesters in the presentdisclosure can, in some embodiments, have crystallization half-times upto infinity. In one aspect of the present disclosure, blends theamorphous copolyesters with other polymers (including other polyestersand copolyesters) are suitable for use provided that the blend has aminimum crystallization half-time of at least about 5 minutes.

Crystallization half-times can be measured using a differential scanningcalorimeter according to the following procedure. A sample of about 10.0mg of the copolyester is sealed in an aluminum pan and heated at a rateof about 320° C./min to about 290° C. and held for about 2 minutes in ahelium atmosphere. The sample is then cooled immediately at a rate ofabout 320° C./min to an isothermal crystallization temperature rangingfrom about 140° C. to about 200° C. with about a 10° C. interval. Thecrystallization half-time at each temperature is then determined as thetime needed to reach the peak on the exothermic curve. The minimumcrystallization half-time is the temperature at which thecrystallization rate is the fastest.

In one embodiment of the present disclosure, the copolyester comprises

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 50 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 50 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 20 to about 60 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms and        -   (ii) about 40 to about 80 mole % of a second modifying            glycol consisting of 2 to 20 carbon atoms,        -   wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and wherein the total mole % of the glycol            component is 100 mole %.

In another embodiment, the copolyester comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   (i) about 50 to about 100 mole % of terephthalic acid            residues;        -   (ii) about 0 to about 50 mole % of aromatic and/or aliphatic            dicarboxylic acid residues having up to 20 carbon atoms; and    -   (b) a glycol component comprising:        -   (i) about 60 to about 100 mole % of a modifying glycol            consisting of 2 to 20 carbon atoms; and        -   (ii) about 0 to about 40 mole % of a second modifying glycol            consisting of 2 to 20 carbon atoms;        -   wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and wherein the total mole % of the glycol            component is 100 mole %.

Unless the context clearly suggests otherwise, the terms “polyester” and“copolyester” are used interchangeably herein. The term “polyester” isintended to include “copolyesters” and is understood to mean a syntheticpolymer prepared by the polycondensation of one or more difunctionalcarboxylic acids (or diacids) with one or more difunctional hydroxylcompounds (or diols). In one embodiment, the difunctional carboxylicacid is a dicarboxylic acid and the difunctional hydroxyl compound is adihydric alcohol such as, for example, glycols and diols.

The term “residue” means any organic structure incorporated into apolymer through a polycondensation reaction involving the correspondingmonomer. The term “repeating unit” means an organic structure having adicarboxylic acid residue (or diacid component) and a diol residue (ordiol component) bonded through a carbonyloxy group. Thus, thedicarboxylic acid residues may be derived from a dicarboxylic acidmonomer or its associated acid halides, esters, salts, anhydrides, ormixtures thereof.

In one embodiment, the copolyesters of the present disclosure areamorphous. In one embodiment, the copolyesters of the present disclosureare essentially amorphous.

In one embodiment, the copolyesters contain repeat units from adicarboxylic acid and a diol, based on 100 mole percent of dicarboxylicacid residues and 100 mole percent of diol residues, respectively.

In one embodiment, the diacid component contains at least about 50 molepercent of the residues of an aromatic dicarboxylic acid having about 8to about 14 carbon atoms. The copolyester may optionally be modifiedwith up to about 50 mole percent, based on 100 mole percent ofdicarboxylic acid residues, of the residues of one or more differentdicarboxylic acids other than an aromatic dicarboxylic acid, such assaturated aliphatic dicarboxylic acids having 4 to 12 carbon atoms andcycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms. Specificexamples of dicarboxylic acids include terephthalic acid, phthalic acid,isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane diacetic acid, diphenyl-4,4′-dicarboxylicacid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacicacid, and the like. The polyester may be prepared from one or more ofthe above dicarboxylic acids.

It should be understood that use of the corresponding acid anhydrides,esters, and acid chlorides of these acids is included in the term“dicarboxylic acid.”

In one embodiment, diol component contains at least about 60 molepercent of the residues of a diol containing 2 to 20 carbon atoms. Inaddition, the diol component may optionally be modified with up to about40 mole percent, based on 100 mole percent of diol residues, of theresidues of one or more other diols. Specific examples of diols includeethylene glycol, diethylene glycol, triethylene glycol, isosorbide,propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol(neopentyl glycol), 2,2,4,4,-tetramethyl-1,3-cyclobutanediol,pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol,3-methyl-pentanediol-(2,4), 2-methylpentanediol-(1,4),2,2,4-tri-methylpentane-diol-(1,3), 2-ethylhexanediol-(1,3),2,2-diethylpropane-diol-(1,3), hexanediol-(1,3),1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane,2,2-bis-(3-hydroxyethoxyphenyl)-propane,2,2-bis-(4-hydroxypropoxyphenyl)-propane, and the like. The polyestermay be prepared from one or more of the above diols.

In one embodiment, the diacid component contains at least about 90 molepercent of the residues of an aromatic dicarboxylic acid having about upto 20 carbon atoms. The copolyester may optionally be modified with upto about 10 mole percent, based on 100 mole percent of dicarboxylic acidresidues, of the residues of one or more different dicarboxylic acidsother than an aromatic dicarboxylic acid, such as saturated aliphaticdicarboxylic acids having 4 to 12 carbon atoms and cycloaliphaticdicarboxylic acids having 8 to 12 carbon atoms. Specific examples ofdicarboxylic acids include terephthalic acid, phthalic acid, isophthalicacid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid,cyclohexane diacetic acid, diphenyl-4,4′-dicarboxylic acid, succinicacid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and thelike. The polyester may be prepared from one or more of the abovedicarboxylic acids.

It should be understood that use of the corresponding acid anhydrides,esters, and acid chlorides of these acids is included in the term“dicarboxylic acid.”

In one embodiment, diol component contains at least about 20 molepercent of the residues of a diol containing 2 to 20 carbon atoms. Inaddition, the diol component may optionally be modified with up to about80 mole percent, based on 100 mole percent of diol residues, of theresidues of one or more other diols. Specific examples of diols includeethylene glycol, diethylene glycol, triethylene glycol, isosorbide,propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol(neopentyl glycol), 2,2,4,4,-tetramethyl-1,3-cyclobutanediol,pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol,3-methyl-pentanediol-(2,4), 2-methylpentanediol-(1,4),2,2,4-tri-methylpentane-diol-(1,3), 2-ethylhexanediol-(1,3),2,2-diethylpropane-diol-(1,3), hexanediol-(1,3),1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane,2,2-bis-(3-hydroxyethoxyphenyl)-propane,2,2-bis-(4-hydroxypropoxyphenyl)-propane, and the like. The polyestermay be prepared from one or more of the above diols.

The polyester may also contain small amounts of trifunctional ortetrafunctional co-monomers such as trimellitic anhydride,trimethylolpropane, pyromellitic dianhydride, pentaerythritol, and otherpolyester forming polyacids or polyols generally known in the art.

In one embodiment, the copolyester comprises (i) a diacid componentcomprising at least about 50 mole percent of residues of terephthalicacid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,isophthalic acid, or mixtures thereof; and (ii) a diol componentcomprising at least about 80 mole percent of residues of a diolcontaining 2 to 10 carbon atoms. In one embodiment, the diacid componentof the copolyester comprises at least about 80 mole percent of theresidues of terephthalic acid, naphthalenedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, isophthalic acid, or mixtures thereof.And in one embodiment, the diol component of the copolyester comprisesthe residues of ethylene glycol, 1,4-cyclohexanedimethanol, diethyleneglycol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, ormixtures thereof.

In another embodiment, the copolyester comprises (i) a diacid componentcomprising at least about 80 mole percent of terephthalic acid residues,and (ii) a diol component comprising at least about 80 mole percent ofthe residues of ethylene glycol and 1,4-cyclohexanedimethanol. In yetanother embodiment, the copolyester comprises (i) a diacid componentcomprising at least about 80 mole percent of terephthalic acid residues,and (ii) a diol component comprising at least about 80 mole percent ofthe residues of ethylene glycol, 1,4-cyclohexanedimethanol, anddiethylene glycol. In yet another embodiment, the copolyester comprises(i) a diacid component comprising at least about 80 mole percent ofterephthalic acid residues, and (ii) a diol component comprising atleast about 80 mole percent of residues of ethylene glycol and neopentylglycol. In yet another embodiment, the copolyester comprises (i) adiacid component comprising at least about 80 mole percent ofterephthalic acid residues, and (ii) a diol component comprising atleast about 80 mole percent of the residues of 1,4-cyclohexanedimethanoland 2,2,4,4-tetramethyl-1,3-cycobutanediol.

Copolyesters useful in the present disclosure can have an inherentviscosity of about 0.40 to about 1.2 dL/g. As used, herein inherentviscosity (or IhV) is the viscosity of a dilute solution of the polymer,specifically IhV is the viscosity of a 60/40 (wt %/wt %)phenol/tetrachloroethane at a concentration of about 0.25 g polyesterper 50 ml solution at about 25° C. or about 30° C. as determined by ASTM4603. This viscosity measurement is representative of the polymer'smolecular weight.

For example, in one embodiment, the copolyester has an inherentviscosity of about 0.45 to about 0.9 dL/g or about 0.60 to about 0.90 asmeasured at about 25° C. using 0.50 grams of polymer per 100 mL of asolvent consisting of 60% by weight of phenol and 40% by weight oftetrachloroethane.

In one embodiment, copolyesters useful in the present disclosure have aglass transition temperature of about 30° C. to about 140° C. Forexample, in one embodiment, the glass transition temperature of thecopolyesters is about 60° C. to about 120° C. In another embodiment,copolyesters useful in the present disclosure have a glass transitiontemperature of at least about 60° C. For example, in one embodiment, thecopolyesters have a glass transition temperature of at least about 90°C. and in another embodiment, the glass transition temperature about100° C.

The copolyester may be prepared by conventional polycondensationprocedures well-known in the art. Such processes include directcondensation of the dicarboxylic acid(s) with the diol(s) or by esterinterchange using a dialkyl dicarboxylate. For example, a dialkylterephthalate such as dimethyl terephthalate is ester interchanged withthe diol(s) at elevated temperatures in the presence of a catalyst. Thepolyesters may also be subjected to solid-state polymerization methods.Suitable methods include the steps of reacting one or more dicarboxylicacids with one or more glycols at a temperature of about 100° C. toabout 315° C. at a pressure of about 0.1 to about 760 mm Hg for a timesufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methodsof producing polyesters, the disclosure of such methods which isincorporated herein by reference.

The copolyesters suitable for use in the present disclosure may beobtained commercially from Eastman Chemical Company.

Polyvinyl Chloride

Any polyvinyl chloride (“PVC”) polymer resin is suitable for use in thepresent disclosure. For example, in one embodiment polyvinyl chloridepolymers useful in the present disclosure include those described in the“Vinyl Chloride Polymers” entry of Kirk-Othmer Encyclopedia of ChemicalTechnology, Vol. 24, 4th ed., (1997) pp. 1017-1053, which isincorporated herein by reference.

In some embodiments, in the present disclosure, suitable PVC polymersinclude homopolymers of polyvinyl chloride resin(s), copolymers ofpolyvinyl chloride resin(s), and mixtures thereof.

In some embodiments, the polyvinylchloride resins are polyvinylchlorideresins, chlorinated polyvinylchloride resins, or alloys thereof.

In some embodiments, copolymers of vinyl chloride are formed by thecopolymerization of vinyl chloride and other monomers or monomer blends.In some embodiments, suitable monomers include vinyl acetate, ethylene,propylene, maleate, methacrylate, acrylate, high alcohol vinyl ester,urethane, chlorinated urethane, methylmethacrylate, and mixturesthereof. In some embodiments, examples of monomer blends includeethylene-vinyl acetate copolymer, acrylonitrile-butadiene-styreneterpolymer, acrylonitrile-butadiene copolymer, and mixtures thereof.

For example, in some embodiments, PVC polymers useful according to thisdisclosure include homopolymers of vinyl chloride and those vinylchloride polymer resins having at least about 70 wt. % repeating unitspolymerized from a vinyl chloride monomer, or at least about 80 wt. %,or at least about 90 wt. %, or even about 95 wt. % or more of repeatingunits polymerized from a vinyl chloride monomer.

In some embodiments, the polyvinyl chloride polymer compositions of thepresent disclosure may comprise repeating units polymerized from a vinylchloride monomer, and may also include comonomers up to about 30 weightpercent of the copolymer from, without limitation, one or more of: theesters of acrylic acid, for example, methyl acrylate, ethyl acrylate,butyl acrylate, octyl acrylate, cyanoethyl acrylate, and the like; vinylesters such as vinyl acetate and vinyl propionate; esters of methacrylicacid, such as methyl methacrylate, ethyl methacrylate, hydroxyethylacrylate, butyl methacrylate, and the like; nitriles, such asacrylonitrile and methacrylonitrile; acrylamides, such as methylacrylamide, N-methylol acrylamide, N-butoxy methacrylamide, and thelike; halogen containing vinyl monomers such as vinylidene chloridevinylidene fluoride, and vinyl bromide; vinyl ethers such as ethylvinylether, chloroethyl vinyl ether and the like; the vinyl ketones, styrenederivatives including α-methyl styrene, vinyl toluene, chlorostyrene;vinyl naphthalene; olefins such as ethylene, butene, isobutylene,propylene and hexene; and other copolymerizable monomers or mixtures ofmonomers having suitable reactivity ratios with vinyl chloride as knownto those skilled in the art.

In one embodiment, the copolymers can include without limitation vinylchloride-vinyl acetate copolymers, vinyl chloride-vinylidene chloridecopolymers, vinyl chloride maleate and fumarate copolymers, vinylchloride-olefin copolymers, vinyl chloride-acrylonitrile copolymers, andthe like, and combinations thereof.

Some embodiments of the present disclosure may employ PVC blends withcrosslinked PVC or crosslinked PVC alone. Crosslinked PVC polymers canbe made by polymerizing vinyl chloride in the presence of crosslinkingmonomers such as the aforementioned diallyl phthalate, trimethylolpropane triacrylate, allyl methacrylate, and the like, as taught in U.S.Pat. Nos. 4,755,699 and 5,248,546, the relevant portions of which areincorporated herein by reference.

The described homopolymers and copolymers are commercially available andmay be produced by any suitable polymerization method includingsuspension, dispersion or blending. For example, in one embodiment,polyvinyl chloride polymers prepared using suspension processes aresuitable for use in the present disclosure.

In some embodiments, the PVC compositions are rigid. Any rigid PVCcompositions are suitable for use in the present disclosure. Forexample, in some embodiments, the rigid compositions are unmodified orunplasticized or the PVC contains small amounts or no plasticizer. Insome embodiments, the rigid compositions contain about 12 phr or less ofplasticizers or plasticizing additives. Whereas, flexible or plasticizedPVC, typically may include plasticizers at levels greater than about 12phr. Thus, rigid PVC according to the present disclosure ischaracterized by a having a higher level of tensile strength thanmodified PVC compositions that are classified as flexible. As usedherein, “parts per hundred parts resin defines the quantity of thecomponents based on the weight of the resin and is abbreviated “phr”.

Also, according to the present disclosure, rigid PVC refers to theproperty of a given compound having more than a certain tensile modulus.For example, PVC may be characterized as rigid when it has a tensilemodulus that exceeds about 105 psi (or about 689 MPa), and semirigidwhen its tensile modulus falls between about 105 psi and about 3000 psi(about 20.7 MPa), and flexible when it has a tensile modulus that isless than about 3000 psi (or about 20.7 MPa) (the tensile modulus valuesare based on standard ASTM conditions of 23° C. and 50% relativehumidity). Therefore, rigid PVC according to the present disclosure mayhave tensile modulus values that vary over a wide range, for example,the tensile modulus values may be from about 800 MPa to about 1000 MPa,or from about 1000 MPa up to about 2000 MPa or even up to 3000 MPa orgreater.

In some the embodiments, the PVC compositions of the present disclosureare suitable for use in a variety of applications including, forexample, building and construction, corner profiles, decking, fencing,railings, soffits, vinyl siding, cladding, window profiles, door frames,siding, fences, gutters, pipes, piping, appliances, electrical andelectronic enclosures, electrical junction boxes, automobile interiorsand exteriors, appliances, office equipment, sign enclosures, medicaldevices, aircraft interiors, and other applications.

In some embodiments, the polyvinyl chloride resin compositions containadditives such as processing aids, plasticizers, stabilizers, impactmodifiers, biocides, flame retardants, foaming agents, blowing agents,ultraviolet light stabilizers, ultraviolet light absorbers, thermalstabilizers, minerals, pigments, dyes, colorants, fillers, waxes, fusionpromoters, antioxidants, antistatic agents, release agents, lubricants,additional resins, heat distortion temperature modifiers, and possiblyother additives. In some embodiments, the amount of polyvinyl chloridein the commercially available rigid polyvinyl chloride resincompositions used are typically is less than about 100%.

Any of the types of PVC resins known in the art can be useful as acomponent of the compositions of the disclosure. In some embodiments,the PVC resins may be in the form of a plastisol or a dry blend.Further, in some embodiments, the compositions of this disclosure caninclude virgin PVC, recycled PVC, such as PVC recycled from variousroofing products, and combinations of virgin and recycled PVC.

In one embodiment, the PVC resins in this disclosure have inherentviscosities as determined by ASTM D1243 ranging from about 0.50 to about1.60 dl/g, or more, for example, about 0.65 to about 1.40 dl/g, forexample, about 0.83 to about 1.00 dl/g.

In one embodiment, the polyvinyl chloride resins have a Tg from about75° C. to about 80° C. In one embodiment, the polyvinyl chloride resinhas a heat deflection temperature (HDT) from about 50° C. to about 75°C.

In one aspect of the present disclosure, when the Tg of the copolyesteris greater than about 90° C., the Tg of the PVC resin composition willincrease and the HDT of the composition will improve.

For example, in some embodiment the polyvinyl chloride articles madeusing the compositions of the present disclosure have a Tg up to 110° C.or a HDT of up to 130° C. while maintaining impact strength. In someembodiments, the articles have an increase in Tg and HDT of at least 3°C. while maintaining impact strength.

In some embodiments, the ratio of PVC resin:copolyester on a weightfraction basis is greater than about 1.

Fibrous Materials and Glass Fibers

The fibrous materials can be formed of any material suitable for theformation of a fiber reinforced article. For example, in one embodimentthe fibrous materials can be polymer resins, including synthetic ornatural polymers, capable of being formed into fibrous materials.Examples of suitable synthetic polymers useful in the present disclosureinclude without limitation polyesters, including polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), polytrimethyleneterephthalate (PTT), poly(1,4-cyclohexylene dimethylene terephthalate)(PCT), and aliphatic polyesters such as polylactic acid (PLA);polyamides, including nylon 6 and nylon 6,6; polyolefins, includingpolypropylene, polyethylene, polybutene, and polymethyl pentene;acrylics; cellulose based materials such as cellulose acetate; and thelike, as well as co- and ter-polymers of these and other suitablepolymers, and combinations thereof. Other exemplary fibrous materialssuitable for use in the present disclosure include, without limitation,fiberglass, glass fibers, carbon fibers, boron fibers, whisker, metallicfibers, inorganic fibers, aramid fibers, basalt fibers, mineral fibers,and the like, and combinations thereof. Exemplary mineral fibers includeWollastanite fibers, fiberglass, and mineral wool. Exemplary whiskerincludes silicon nitride whisker, silicon trinitride whisker, magnesiumsulfate whisker, barium titanate whisker, silicon carbide whisker andboron whisker. Exemplary metallic fibers include fibers of soft steel,stainless steel, steel and alloys thereof, brass, aluminum and alloysthereof and lead. Exemplary inorganic fibers include various fibers ofrock wool, zirconia, alumina silica, potassium titanate, bariumtitanate, titanium oxide, silicon carbide, alumina, silica and blastfurnace slag.

In one embodiment, glass fibers are used as the fibrous material.Exemplary glass fibers include ordinary glass fibers as well as glassfibers coated with metals such as nickel and copper, or silane treatedglass fibers. Other examples of the glass fibers suitable for use in thepresent disclosure include filaments obtained by melt-spinning glasssuch as E glass (electrical glass), C glass (chemical glass), A glass(alkali glass), S glass (high strength glass), M glass (modulus or highstiffness), D glass (low dielectric glass), E-CR glass(electrical/chemical resistant), R glass (reinforcement glass), T glass(thermal insulator glass), and alkali-proof glass.

In one embodiment, the glass fibers have a diameter of about 1 to about25 μm, or from about 8 to about 20 μm. In one embodiment, the glassfibers have a length of about 0.1 to about 50.0 mm or from about 0.1 toabout 25.0 mm. In another embodiment, the glass fibers have a length ofabout 0.4 to about 12.0 mm. In another embodiment, the glass fibers havea length of about 0.4 to about 4.0 mm. In another embodiment, the glassfibers have a length of about 4.0 to about 50.0 mm or from about 4.0 toabout 25.0 mm. In another embodiment, the glass fibers are long fibersor greater than about 4 mm. In yet another embodiment, the glass fibersare short fibers or less than about 4 mm.

In one embodiment, the fiber reinforced polyvinyl chloride compositionsof the present disclosure have a content of fibrous materials of up toabout 65% by weight based on the total weight of the composition. In oneembodiment, the fiber reinforced polyvinyl chloride compositions of thepresent disclosure have a glass fiber content of up to about 65% byweight based on the total weight of the composition. In one embodiment,the fiber reinforced polyvinyl chloride compositions of the presentdisclosure have a content of fibrous materials of up to about 40% byweight based on the total weight of the composition. In one embodiment,the glass fiber content is up to about 40% by weight based on the totalweight of the composition. In one embodiment, the content of the fibrousmaterials is about 30% to about 65% or about 40% to about 65% by weightbased on the total weight of the composition. In one embodiment, thecontent of the fibrous materials is greater than about 30% by weightbased on the total weight of the composition. In one embodiment, thecontent of the fibrous materials is at least about 60% by weight basedon the total weight of the composition. In another embodiment, thecontent of the fibrous materials is at least about 40% by weight basedon the total weight of the composition. In one embodiment, the contentof the fibrous materials is about 1% to about 65% by weight based on thetotal weight of the composition. In one embodiment, the glass fibercontent is about 30% to about 65% or about 40% to about 65% by weightbased on the total weight of the composition. In one embodiment, theglass fiber content is greater than about 30% by weight based on thetotal weight of the composition. In one embodiment, the glass fibercontent is at least about 60% by weight based on the total weight of thecomposition. In another embodiment, the glass fiber content is at leastabout 40% by weight based on the total weight of the composition. In oneembodiment, the glass fiber content is about 1% to about 65% by weightbased on the total weight of the composition. In one embodiment, thecontent of the fibrous materials is about 1% to about 40% by weightbased on the total weight of the composition. In one embodiment, thecontent of the fibrous materials is about 30% to about 65% or about 40%to about 65% by weight based on the total weight of the composition. Inone embodiment, the content of the fibrous materials is greater thanabout 30% by weight based on the total weight of the composition. In oneembodiment, the content of the fibrous materials is at least about 60%by weight based on the total weight of the composition. In anotherembodiment, the content of the fibrous materials is at least about 40%by weight based on the total weight of the composition. In oneembodiment, the content of the fibrous materials is about 1% to about65% by weight based on the total weight of the composition. In oneembodiment, the content of the fibrous materials is about 1% to about40% by weight based on the total weight of the composition.

The fibrous materials and in some embodiments, the glass fibers, areincorporated into the PVC resins in the present disclosure to improvethe physical properties such as tensile and flexural strength, tensileand flexural modulus, coefficient of linear thermal expansion and heatdistortion temperature. The present disclosure uses copolyesters tofacilitate the incorporation of the fibrous materials into the PVCcompositions.

In some embodiments, when the fibrous materials and copolyesters areadded at the appropriate concentrations to PVC compositions, theresulting compositions have increased tensile strength and modulus asdetermined by ASTM D638 and increased flexural strength and modulus asdetermined by ASTM D790.

The copolyesters in the present disclosure are miscible in PVC and arealso compatible with the fibrous materials, including in someembodiments, glass fibers. The term “miscible” refers to blends of twoor more polymers that are homogenous on molecular level and behave as asingle-phase mixture, exhibiting only one glass transition temperature(Tg).

The copolyesters in the present disclosure “wet out” the fibrousmaterials and enable incorporation of the fibrous materials into the PVCcompositions; and when properly incorporated the fibrous materialsimprove the physical properties of the PVC compositions. Without beingbound by any theory, the copolyesters of the present disclosure “wetout” the fibrous materials including in some embodiments, the glassfibers due to the higher surface energies of copolyesters of the presentdisclosure.

The resulting fiber reinforced PVC compositions disclosed herein can beprocessed on any standard PVC processing equipment, at any standard PVCprocessing temperatures (about 170° C. to about 230° C.), and using anystandard PVC processing methods such as extrusion, injection molding,profile extrusion and sheet extrusion.

In some embodiments, the copolyesters of the present disclosure haveTg's from about 55° C. to about 120° C. In some embodiments, thecopolyesters of the present disclosure have Tg's of at least about 60°C. and higher. In some embodiments, the copolyesters of the presentdisclosure have Tg's of at least about 90° C. and higher. In someembodiments, the copolyesters of the present disclosure have Tg's of atleast about 100° C. and higher. In some embodiments, the copolyesters ofthe present disclosure have Tg's of at least about 110° C. and higher.

In some instances, the bonding between the fibrous materials and thecopolyesters can depend on the surface composition, structure andproperties of the fibrous materials and the copolyesters.

In some instances, the bonding between the glass fibers and thecopolyesters can depend on the surface composition, structure andproperties of the glass fibers and the copolyesters.

For example, in some embodiments, chemical surface treatments are usedon the glass fibers to decrease the polar nature of the glass fibers toallow them to wet out on lower surface energy polymers. In someembodiments, these chemical surface treatments involve the use oforganosilanes. The Si—OH functionality of the organosilane adheres tothe glass fiber and the organic component of the organosilane is morecompatible with the polymer matrix. The surface energies are oftenmeasured through microscopic contact angle measurements (goniometry) ofa polar liquid, typically water, and a less-polar liquid such as hexaneor diiodomethane.

For higher adhesion properties, a material must ‘wet out’ the surface tobe bonded. To ‘wet out’ means that the material flows and covers thesurface to maximize the contact area and the attractive forces betweenthe material and the bonding surface. In most instances, a lower surfaceenergy material, such as water, will wet out a higher energy surface.

In some instances, for a material to wet out a surface, the surfaceenergy of the material must be as low as or lower than the surfaceenergy of the substrate to be bonded. Alternatively, the surface energyof the substrate could be raised. In certain aspects of the presentdisclosure, it is easier for the higher surface energy copolyesters towet out the glass fibers than lower surface energy polymers such aspolyolefins and PVC.

In another aspect of the present disclosure, during the wetting out andprocessing of the glass fibers having a lower viscosity polymer matrixprevents damage or breakage of the glass fibers during processing. Manyplastics reinforced with glass fibers use crosslinkable thermosetmaterials like epoxies or vinyl esters because they are in liquid formand ease the impregnation and wetting of the fiber bundles to addressthese concerns. These crosslinking materials are not required in certainembodiments of the present disclosure. Typically, thermoplastic glassfilled materials have utilized crystalline polymers such as nylon 6 and6,6 and polybutylene terephthalate which have low melt viscosities atstandard processing temperatures, and thus wetting out the glass fibersmore readily and minimizing glass breakage during processing. Thecopolyesters used in certain embodiments of the present disclosure, donot have distinct melting points but instead will undergo a decrease inviscosity as the processing temperatures increase past its glasstransition temperature. Lower viscosity copolyesters can be obtained byusing copolyesters with lower molecular weights.

In one embodiment of the present disclosure, the copolyesters have aviscosity range of about 1,000 to about 1,000,000 poise measured at atemperature of about 170° C. to about 200° C. and at a shear rate of 10s⁻¹, or from about 10,000 to about 500,000 poise or from about 20,000 toabout 300,000 poise. The viscosity measurements in this aspect of theinvention are made by performing small amplitude oscillatory shear(SAOS) experiments using a Rheometrics RDA II rheometer and performingfrequency sweeps over the range of 1 to 400 s−1 at multiple temperaturesabove the Tg as determined by ASTM D4440. In some embodiments, theviscosities are measure at the PVC processing temperatures of about 170to about 230° C.

In one embodiment of the present disclosure, copolyesters have acrystallization half time of greater than about 5 minutes, a glasstransition temperature of at least about 60° C. or higher, a viscosityrange of about 1,000 to about 1,000,000 poise measured at a temperatureof about 170° C. to about 230° C. and at a shear rate of 10 s⁻¹, and asurface energy of equal to or greater than about 40 dynes per cm and arecombined with fibrous materials at a fibrous material content of up toabout 65% by weight based on the total weight of the composition. Thesurface energy measurements in this disclosure are determined by ASTMD7490.

In another embodiment of the present disclosure, copolyesters have acrystallization half time of greater than about 5 minutes, a glasstransition temperature of at least about 90° C. or higher and aviscosity range of about 1,000 to about 1,000,000 poise measured at atemperature of about 170° C. to about 230° C. and at a shear rate of 10s⁻¹, and a surface energy of equal to or greater than about 40 dynes percm are about combined with fibrous materials at a fibrous materialcontent of at least about 40% by weight based on the total weight of thecomposition.

In one embodiment, the copolyesters are added to PVC compositions tocreate compositions of about 1% to about 40% fibrous material content,or about 1% to about 65% fibrous material content based on the totalweight of the composition. In some embodiments, the polyvinyl chloridecompositions are rigid.

In one embodiment of the present disclosure, copolyesters have acrystallization half time of greater than about 5 minutes, a glasstransition temperature of at least about 60° C. or higher, a viscosityrange of about 1,000 to about 1,000,000 poise measured at a temperatureof about 170° C. to about 230° C. and at a shear rate of 10 s⁻¹, and asurface energy of equal to or greater than about 40 dynes per cm and arecombined with glass fibers up to about 65% by weight based on the totalweight of the composition. The surface energy measurements in thisdisclosure are determined by ASTM D7490.

In another embodiment of the present disclosure, copolyesters have acrystallization half time of greater than about 5 minutes, a glasstransition temperature of at least about 90° C. or higher and aviscosity range of about 1,000 to about 1,000,000 poise measured at atemperature of about 170° C. to about 230° C. and at a shear rate of 10s⁻¹, and a surface energy of equal to or greater than about 40 dynes percm are about combined with glass fibers at a glass fiber content of atleast about 40% by weight based on the total weight of the composition.

In one embodiment, the copolyesters are added to PVC compositions tocreate compositions of about 1% to about 40% glass fiber content, orabout 1% to about 65% glass fiber content based on the total weight ofthe composition. In some embodiments, the polyvinyl chloridecompositions are rigid.

In some embodiments; the PVC resins are combined with other additivessuch as processing aids, plasticizers, stabilizers, impact modifiers,biocides, flame retardants, foaming agents, blowing agents, thermalstabilizers, UV stabilizers, UV absorbers, minerals, pigments, dyes,colorants, fibers, fillers, waxes, fusion promoters, antioxidants,antistatic agents, release agents, lubricants, additional resins, heatdistortion temperature modifiers and possibly other additives,

One embodiment of the present disclosure is a method of producing afiber reinforced polyvinyl chloride composition comprising: compoundingfibrous materials with a miscible admixture of at least one polyvinylchloride resin and at least one copolyester which comprises: (a) adicarboxylic acid component comprising: (i) about 90 to about 100 mole %of terephthalic acid residues; (ii) about 0 to about 10 mole % ofaromatic and/or aliphatic dicarboxylic acid residues having up to 20carbon atoms; and (b) a glycol component comprising: (i) about 20 toabout 60 mole % of a modifying glycol consisting of 2 to 20 carbon atomsand (ii) about 40 to about 80 mole % of a second modifying glycolconsisting of 2 to 20 carbon atoms, to produce a viscous thermoplasticmaterial, extruding the compound through a die to produce pellets; andintroducing the pellets into a calendering, extrusion or injectionmolding process to produce polyvinyl chloride articles.

Another embodiment of the present disclosure is a method of producing afiber reinforced polyvinyl chloride composition comprising: compoundingglass fibers with at least one copolyester which comprises: (a) adicarboxylic acid component comprising: (i) about 90 to about 100 mole %of terephthalic acid residues; (ii) about 0 to about 10 mole % ofaromatic and/or aliphatic dicarboxylic acid residues having up to 20carbon atoms; and (b) a glycol component comprising: (i) about 20 toabout 60 mole % of a modifying glycol consisting of 2 to 20 carbon atomsand (ii) about 40 to about 80 mole % of a second modifying glycolconsisting of 2 to 20 carbon atoms, to produce a viscous thermoplasticmaterial, mixing the compounded composition with a polyvinyl chlorideresin to create a polyvinyl chloride composition of about 1% to about65% glass fiber content based on the total weight of the composition;extruding the polyvinyl chloride composition through a die to producepellets; and introducing the pellets into a calendering, extrusion orinjection molding process to produce polyvinyl chloride articles.

One embodiment of the present disclosure is a method of producing afiber reinforced polyvinyl chloride composition comprising: compoundingfibrous materials with a miscible admixture of at least one polyvinylchloride resin and at least one copolyester which comprises: (a) adicarboxylic acid component comprising: (i) about 50 to about 100 mole %of terephthalic acid residues; (ii) about 0 to about 50 mole % ofaromatic and/or aliphatic dicarboxylic acid residues having up to 20carbon atoms; and (b) a glycol component comprising: (i) about 60 toabout 100 mole % of a modifying glycol consisting of 2 to 20 carbonatoms and (ii) about 0 to about 40 mole % of a second modifying glycolconsisting of 2 to 20 carbon atoms, to produce a viscous thermoplasticmaterial, extruding the compound through a die to produce pellets; andintroducing the pellets into a calendering, extrusion or injectionmolding process to produce polyvinyl chloride articles.

Another embodiment of the present disclosure is a method of producing afiber reinforced polyvinyl chloride composition comprising: compoundingglass fibers with at least one copolyester which comprises: (a) adicarboxylic acid component comprising: (i) about 50 to about 100 mole %of terephthalic acid residues; (ii) about 0 to about 50 mole % ofaromatic and/or aliphatic dicarboxylic acid residues having up to 20carbon atoms; and (b) a glycol component comprising: (i) about 60 toabout 100 mole % of a modifying glycol consisting of 2 to 20 carbonatoms and (ii) about 0 to about 40 mole % of a second modifying glycolconsisting of 2 to 20 carbon atoms, to produce a viscous thermoplasticmaterial, mixing the compounded composition with a polyvinyl chlorideresin to create a polyvinyl chloride composition of about 1% to about65% glass fiber content based on the total weight of the composition;extruding the polyvinyl chloride composition through a die to producepellets; and introducing the pellets into a calendering, extrusion orinjection molding process to produce polyvinyl chloride articles.

In some embodiments, the fiber reinforced PVC compositions of thepresent disclosure are used to make articles such as films, sheets,profiles or injection molded articles and parts.

The compositions of this disclosure are useful as molded plastic partsor as solid plastic objects. In some embodiments, the films, sheets,profiles, and injection molded articles and parts can be made using anyextrusion process including extrusion processes whereby pellets areeither blended together (when using concentrated ingredients) or addeddirectly to an extruder (when using a fully compounded composition). Insome embodiments, the films, profiles and sheets can be made using anycalendering process.

In some embodiments, melt processing of the compositions of the presentdisclosure involves extrusion using any equipment known in the artincluding, without limitation, twin screw extruders, single screwextruders, high intensity batch mixers, Banbury mixers, Brabendermixers, roll mills, ko-kneaders or planetary gear extruder. The shearenergy during the mixing is dependent on the combination of equipment,blade design, rotation speed (rpm), and mixing time. The shear energyshould be sufficient to disperse the fibrous materials throughout thecopolyester.

In some embodiments, the fibrous materials, copolyesters, polyvinylchloride resins and additives can be combined in any order during theprocess. In one embodiment, the fibrous materials are premixed with thecopolyesters and/or other additives. Next, the copolyesters containingthe fibrous materials are then mixed with the polyvinyl chloride resinand/or other additives.

The disclosure further relates to articles of manufacture comprising thefilm(s) and/or sheet(s) containing polyvinyl chloride compositionsdescribed herein. In embodiments, the films and/or sheets of the presentdisclosure can be of any thickness which would be apparent to one ofordinary skill in the art.

The disclosure further relates to the molded articles described herein.The methods of forming the poly vinyl chloride compositions into moldedarticles can include any known methods in the art. Examples of moldedarticles of the disclosure including but not limited to injection moldedarticles, and extrusion articles such as sheet, film, or profiles.Methods of making molded articles include but are not limited toinjection molding and extrusion.

The compositions of the copolyesters and fibrous materials (or glassfibers) of the present disclosure can be made into pellets using anystandard procedure.

For example, the pellets of present disclosure can be made the followingways. In one embodiment, the copolyesters and fibrous materials (orglass fibers) can be combined using a twin screw compounding line. Thecopolyester pellets and fibrous materials (or glass fibers) are fedseparately, or together, into the throat of the extruder. Thecopolyester melts and combines with the fibrous materials (or glassfibers) to produce a viscous, reinforced thermoplastic material.

In one embodiment, the copolyesters and the fibrous materials (or glassfibers) can be mixed using loss-in-weight feeders. The rotation of thetwo screws melts the copolyesters and mixes with the fibrous materials(or glass fibers). The mixtures are then extruded through a die toproduce multiple strands. The strands can be fed through a water troughto cool the pellets. Upon exiting the water trough, the strands aredried and fed into a dicer to cut the strands into pellets.Alternatively, the mixture can be extruded through a circular flat platedie with multiple openings into water. The flat plate die has a rotatingcutter that slices the strands as they extrude from the die to producepellets. The continuous flow of water cools the pellets and transportsthem to a drying section, typically a centrifuge is then used toseparate the pellets from the water.

In one embodiment, the copolyesters and fibrous materials (or glassfibers) can be combined using as a two-rotor continuous compoundingmixer (such as a Farrell Continuous Mixer). The fibrous materials (orglass fibers) be fed into the throat of the extruder and melted toproduce a viscous thermoplastic material. The copolyesters can bepre-blended with the fibrous materials (or glass fibers) and added tothe extruder with a loss-in-weight feeder. The output rate of the mixeris controlled by varying the area of a discharge orifice. The melt canbe sliced off into ‘loaves’ and fed to a two roll mill or the throat ofa single screw extruder. In the case of the melt being fed to a two-rollmill, the melt covers one of the rolls and strip can be fed to thethroat of a single screw extruder. The mixture is then extruded througha die to produce multiple strands. The strands can be fed through awater trough to cool the pellets. Upon exiting the water trough, thestrands are dried and fed into a dicer to cut the strands into pellets.Alternatively, the mixture can be extruded through a circular flat platedie with multiple openings into water. The flat plate die has a rotatingcutter that slices the strands as they extrude from the die to producepellets. The continuous flow of water cools the pellets and transportsthem to a drying section, typically a centrifuge to separate the pelletsfrom the water. In the case of the ‘loaves’ being fed to a single screwextruder, the mixture is extruded through a die to produce multiplestrands. The strands can be fed through a water trough to cool thepellets. Upon exiting the water trough, the strands are dried and fedinto a dicer to cut the strands into pellets. Alternatively, the mixturecan be extruded through a circular flat plate die with multiple openingsinto water. The flat plate die has a rotating cutter that slices thestrands as they extrude from the die to produce pellets. The continuousflow of water cools the pellets and transports them to a drying section,typically a centrifuge to separate the pellets from the water.

In some embodiments, the copolyester and fibrous materials (or glassfibers) compositions can be combined in a plastics compounding line suchas a Banbury batch type mixer. In these embodiments, the copolyestersand fibrous materials (or glass fibers) can be fed into the Banbury—typehigh-intensity mixer and a ram lowered to compress the mixture into themixing chamber. Two rotating mixer blades melt the pellets and melt thecopolyester and fibrous materials (or glass fibers). When the desiredtemperature is reached, a door is opened in the bottom of the mixer andthe mixture is dropped two a two roll mill. A ribbon from the two rollmill can then be fed to a single screw extruder. The mixture is thenextruded through a die to produce multiple strands. The strands can befed through a water trough to cool the pellets. Upon exiting the watertrough, the strands are dried and fed into a dicer to cut the strandsinto pellets. Alternatively, the mixture can be extruded through acircular flat plate die with multiple openings into water. The flatplate die has a rotating cutter that slices the strands as they extrudefrom the die to produce pellets. The continuous flow of water cools thepellets and transports them to a drying section, typically a centrifugeto separate the pellets from the water.

The present disclosure envisions combining the aforementionedcopolyester/fibrous materials (or glass fibers) composition with a PVCcomposition in melt-based processes, as follows: one embodiment entailsfirst combining the copolyester fibrous materials (or glass fibers)composition with PVC to produce a pellet, using single screw, twinscrew, or other compounding techniques well established in the art. Thisreinforced PVC pellet can then be used to produce useful articles in asecond step, using other melt-based processes such as injection molding,sheet or film extrusion, calendering, extruded profiles, or othermethods well established in the art.

Another embodiment of the disclosure consists of directly combining thecopolyester/fibrous materials (or glass fibers) composition and a PVCcomposition to produce a flat sheet or profile using an extrusionprocess—all in a single step. In one embodiment, this can beaccomplished several ways by separately adding the copolyester/fibrousmaterials (or glass fibers) composition as described above and addedseparately to the throat of a single or twin screw extruder. In anotherembodiment, a blend of the copolyester/fibrous materials (or glassfibers) composition and PVC composition can be preblended and added tothe throat of a single or twin screw extruder. The blended mixture insome embodiments is conveyed and compressed by the screw(s) down theextruder barrel to melt the mixture and discharge the melt from the endof the extruder. The melt can then be fed through a die to create acontinuous flat sheet or an into a profile die to create a continuousshape. In the embodiments using the flat sheet die, the melt is extrudedonto a series of metal rolls, typically three, to cool the melt andimpart a finish onto the sheet. The flat sheet is then conveyed in acontinuous sheet to cool the sheet. It can then be trimmed to thedesired width and then either rolled up into a roll or sheared or sawedinto sheet form. A flat sheet can also be formed into a shape throughmechanical means to form a desired shape and then cooled either byspraying with water, through a water trough or by blowing air on theprofile. It can then be sawed or sheared to the desired length.

In embodiments using a profile die, the die is designed to produce thedesired shape of the article. After exiting the die, it can then becooled either by spraying with water, through a water trough or byblowing air on the profile. It can then be sawed or sheared to thedesired length.

Another embodiment of the disclosure consists of combining acopolyester/fibrous material (or glass fibers) composition and a PVCcomposition to produce an injection molded article. This can beaccomplished several ways by separately adding the copolyester/fibrousmaterials (or glass fibers) composition as described above and addedseparately to the throat of the injection molding machine. In anotherembodiment, a blend of the copolyester/fibrous materials (or glassfibers) composition and PVC composition can be preblended and addeddirectly to the throat of the injection molding machine. The blendedmixture, in some embodiments, is conveyed and compressed by the screw(s)down the extruder barrel to melt the mixture and discharge the melt fromthe end of the extruder. Once the pellets reach the desired temperature,a gate is opened at the end of the extruder and the melted plastic ispumped by the screw into a heated mold to form an article of the desiredshape. Once the mold is filled, a coolant is pumped through the mold tocool it and the melted plastic. Once the plastic has solidified, themold is opened and the article is removed from the mold.

Useful applications for these fiber reinforced PVC compositions caninclude many building and construction applications such as cornerprofiles, decking, fencing, railings, window profiles and other interiorand exterior applications.

Other applications for these fiber reinforced PVC compositions caninclude uses in appliances, electrical and electronic enclosures, signenclosures, automotive applications, aircraft interiors, and other hightemperature applications where rigid PVC formulations have been limiteddue to their lower tensile strength and modulus and flexural strengthand modulus.

For example, in some embodiments, the PVC articles of this disclosureare used in the following applications: building and construction,corner profiles, decking, fencing, railings, soffits, vinyl siding,cladding, window profiles, door frames, siding, fences, gutters, pipes,piping, electrical and electronic enclosures, electrical junction boxes,automobile interiors and exteriors, appliances, office equipment, signenclosures, medical devices, aircraft interiors, and other hightemperature applications. In some embodiments, the polyvinyl chloridearticles are rigid.

This disclosure can be further illustrated by the following examples,although it will be understood that these examples are included merelyfor purposes of illustration and are not intended to limit the scope ofthe disclosure unless otherwise specifically indicated.

Examples

The following tables summarize the experimental results of thedisclosure and counterexamples:

TABLE 1 Tensile Tensile Max Flexural Flexural Unmatched HDT % % %Strength Modulus Strain at Strength Modulus IZOD (at 1.8 DescriptionGlass Copolyester PVC Material (psi) (psi × 10⁶) break % (psi) (psi ×10⁶) (ft-lbs/in) MPa) Regrind PVC 0  100% 0% LGF 6,489 0.344 4.15911,042 0.386 DNE 33% LGF60- Eastar ™ 19.8 13.2 67 20% LGF, 10,374 0.8901.517 14,724 0.872 5.6 5011 NAT + 67% PVC Eastar 5011 66% LGF60 - Eastar39.6 26.4 34 40% LGF, 12,189 1.551 1.056 17,456 1.503 4.5 5011 NAT + 34%PVC Eastar 5011 33% LGF60 -Embrace ™ 19.8 13.2 67 20% LGF, 10,696 0.9491.464 15,195 0.949 5.8 LV NAT + 67% PVC Embrace LV 66% LGF60 - Embrace39.6 26.4 34 40% LGF, 12,446 1.571 1.042 17,842 1.498 4.6 LV NAT + 34%PVC Embrace LV 66% LGF60 - Tritan ™ 39.6 26.4 34 40% LGF, 13,256 1.0802.093 18,591 1.609 6.0 85 TX1500 + 34% PVC Embrace LV 33% LGF60 - Tritan19.8 13.2 67 20% LGF, 11,349 0.738 2.489 16,976 1.062 6.7 78 TX1500 +67% PVC Embrace LV

Table 1 is a summary of the physical property data for PVC compositionswith and without various levels of glass fiber reinforced copolyesterpellets. A blend of 60% long glass fibers and 40% of three differentcopolyester resins, Embrace™ LV, Eastar™ 5011, and Tritan™ TX1500, wereprepared using a pultrusion-type of process, where continuous glassfiber strands were pulled through a cross-head die containing saidcopolyester. In a second step, PVC composite samples were then preparedby adding the glass reinforced copolyester pellets to the rigid PVCcomposition at two different levels to produce samples with 20% and 40%glass fibers content in the final composition. Bars of the finalcompositions were injection molded into samples and these samples weretested for the following physical properties: tensile properties (ASTMD638), flexural properties (ASTM D790), unnotched IZOD strength (ASTMD256), and in some examples HDT (ASTM D 648 at 1.8 MPa test condition).

The physical property test results show that each of the compositionswith approximately 20% glass fiber increased the properties of theunfilled PVC as follows:

-   -   Tensile strength increased by about 60-75%    -   Tensile modulus increased by about 110-180%    -   The flexural strength increased by about 30-55%    -   The flexural modulus increased by about 125-175%

The physical property test results show that each of the compositionswith approximately 40% glass fiber increased the properties of theunfilled PVC as follows

-   -   Tensile strength increased by about 85-105%    -   Tensile modulus increased by about 200-350%    -   The flexural strength increased by about 55-70%    -   The flexural modulus increased by about 285-315%

The HDT was measured for some of the copolyesters with a Tg greater than90° C. In some of these examples, the resulting compositions showed asignificant boost in HDT when the Tritan™ copolyester (TX1500) was addedto the blends. Unfilled rigid PVC typically has an HDT of 70-75° C. atthe highest range. In these examples, the Tritan copolyester incombination with 20 and 40% glass fiber respectively enabled HDT valuesof 78 and 85° C. (or a 3-10° C. increase over standard rigid PVCformulations). Without being bound by any theory, the Tritan copolyester(TX1500) in these examples, seems to serve as a glass compatibilizer andan HDT booster, because of the higher glass transition temperature (Tg)of the Tritan resin (Tg ˜110° C.).

TABLE 2 Dispersive SE Polar SE Total SE dynes/cm dynes/cm dynes/cmTritan ™ TX2000 39.5 3.6 43.1 Eastar ™ 5011 43.6 4.1 47.7 Embrace ™ LV45.3 3.3 48.6 Rigid PVC Literature 39

Table 2 summarizes the surface energy data determined by contact anglemeasurements using a goniometer and a literature value for rigid PVC.The data shows that the three copolyester resins tested, Tritan™ TX2000,Embrace™ LV and Eastar™ 5011, all have surface energies greater thanrigid PVC. The higher surface energies for the copolyester resinsindicates that the copolyesters will wet out the glass fibers morereadily that rigid PVC alone because the rigid PVC has a lower surfaceenergy.

TABLE 3 Rheology Data Viscosity Viscosity Viscosity at 1 at 400 at 10rad/s rad/s rad/s Material Temperature (Poise) (Poise) (Poise) Rigid PVC170 593,056 6,586 108,759 Rigid PVC 180 352,838 6,489 82,027 Rigid PVC190 221,955 6,325 62,324 Eastar ™ 5011 170 119,470 19,138 93,455 Eastar5011 180 64,659 15,046 55,926 Eastar 5011 190 37,286 11,719 34,271Embrace ™ LV 170 197,445 20,690 128,657 Embrace LV 180 119,654 17,27886,156 Embrace LV 190 75,871 14,396 59,148 Tritan ™ TX2000 170 3,349,96046,842 839,097 Tritan TX2000 180 1,721,570 40,267 591,415 Tritan TX2000190 868,995 34,978 398,428 Tritan TX2000 220 126,017 20,476 100,357Tritan TX2000 240 45,052 13,497 41,440 Tritan TX1500 170 746,841 28,612384,575 Tritan TX1500 180 383,803 24,901 249,083 Tritan TX1500 190204,249 21,546 154,945 Tritan TX1500 220 39,032 12,637 36,195 TritanTX1500 240 15,372 7,897 14,845

Table 3 illustrates the viscosity data at 170° C., 180° C. and 190° C.at various shear rates (1, 10, and 400 s⁻¹) determined using parallelplate rheometry for Tritan™ TX2000, Tritan TX1500, Embrace™ LV, Eastar™5011 and a rigid PVC composition. The data shows the distinctdifferences in viscosity for the copolyester resins in contrast to PVC.As shown, Tritan TX2000 is the most viscous copolyester and Eastar 5011is the least viscous. The viscosity of Eastar 5011 is closer to theviscosity of the rigid PVC composition. Each of these copolymers, TritanTX2000, Tritan TX1500, Embrace LV, and Eastar 5011 act as carriers andcompatibilizers for incorporating the glass fibers into rigid PVC.However, in instances where it is necessary to minimize glass fiberbreakage during incorporation, lower viscosity copolyesters such asEastar 5011 can be used. Based on the data in Table 3, it appears thatcopolyesters having viscosity values of 1,000 to 1,000,000 poise,measured at shear rates of 10 s⁻¹ and at PVC processing conditions(170-230° C.) are suitable for this invention.

The invention claimed is:
 1. A polyvinyl chloride composition comprisinga polyvinyl chloride resin, fibrous materials and at least onecopolyester which comprises: (a) a dicarboxylic acid componentcomprising: (i) about 50 to about 100 mole % of terephthalic acidresidues; (ii) about 0 to about 50 mole % of aromatic and/or aliphaticdicarboxylic acid residues having up to 20 carbon atoms; and (b) aglycol component comprising: (i) about 60 to about 100 mole % of amodifying glycol consisting of 2 to 20 carbon atoms; and (ii) about 0 toabout 40 mole % of a second modifying glycol consisting of 2 to 20carbon atoms; wherein the total mole % of the dicarboxylic acidcomponent is 100 mole %, and wherein the total mole % of the glycolcomponent is 100 mole %, and wherein the copolyester is amorphous andhas a T_(g) of about 90° C. or higher.
 2. The polyvinyl chloridecomposition of claim 1, wherein the Tg of the copolyester is at leastabout 90° C. or higher.
 3. The polyvinyl chloride composition of claim1, wherein the Tg of the copolyester is at least about 100° C. orhigher.
 4. The polyvinyl chloride composition of claim 1, wherein thecopolyester has a crystallization half time of about 5 minutes orgreater.
 5. The polyvinyl chloride composition of claim 1, wherein thecopolyester has a crystallization half time of about 10 minutes orgreater.
 6. The polyvinyl chloride composition of claim 1, wherein thefibrous materials are glass fibers.
 7. The polyvinyl chloridecomposition of claim 1, wherein the fibrous materials are fiberglass,glass fibers, carbon fibers, boron fibers, whisker, metallic fibers,inorganic fibers, aramid fibers, basalt fibers, mineral fibers, andcombinations thereof.
 8. The polyvinyl chloride composition of claim 1,wherein the copolyester is about 1 to about 100 parts per hundred resin(phr) based on the content of the polyvinyl chloride resin in thecomposition.
 9. The polyvinyl chloride composition of claim 6, whereinthe glass fiber content is up to about 65% by weight based on the totalweight of the composition.
 10. The polyvinyl chloride composition ofclaim 6, wherein the glass fiber content is up to about 40% by weightbased on the total weight of the composition.
 11. The polyvinyl chloridecomposition of claim 6, wherein the glass fiber content is about 40 to65% by weight based on the total weight of the composition.
 12. Thepolyvinyl chloride composition of claim 6, wherein the glass fibercontent is about 30 to 65% by weight based on the total weight of thecomposition.
 13. The polyvinyl chloride composition of claim 1, whereinthe content of the fibrous materials is greater than about 30% by weightbased on the total weight of the composition.
 14. The polyvinyl chloridecomposition of claim 6, wherein the glass fiber content is at leastabout 60% by weight based on the total weight of the composition. 15.The polyvinyl chloride composition of claim 1, wherein the content ofthe fibrous materials is about 1% to about 65% by weight based on thetotal weight of the composition.
 16. The polyvinyl chloride compositionof claim 1, wherein the ratio of PVC:copolyester on a weight fractionbasis is greater than about
 1. 17. The polyvinyl chloride composition ofclaim 1, wherein the content of the fibrous materials is at least about40% by weight based on the total weight of the composition.
 18. Thepolyvinyl chloride composition of claim 6, wherein the glass fibers areshort fibers and have a length of less than about 4 mm.
 19. Thepolyvinyl chloride composition of claim 6, wherein the glass fibers arelong fibers and have a length of greater than about 4 mm.
 20. Thepolyvinyl chloride composition of claim 6, wherein the copolyester has aviscosity range of about 1,000 poise to about 1,000,000 poise measuredat a temperature of about 170° C. to about 230° C. and at a shear rateof 10 s⁻¹, and a surface energy of equal to or greater than about 40dynes per cm, and wherein the glass fiber content is up to about 65% byweight based on the total weight of the composition.
 21. The polyvinylchloride composition of claim 1, wherein said polyvinyl chloride resinis a polyvinyl chloride resin, a chlorinated polyvinyl chloride resin,or alloys thereof.
 22. The polyvinyl chloride composition of claim 1,wherein said composition further comprising at least one additiveselected from the group consisting of processing aids, plasticizers,stabilizers, impact modifiers, biocides, flame retardants, foamingagents, blowing agents, thermal stabilizers, UV stabilizers, UVabsorbers, minerals, pigments, dyes, colorants, fillers, fibers, waxes,fusion promoters, antioxidants, antistatic agents, release agents,lubricants, additional resins, and heat distortion temperaturemodifiers.
 23. An article formed by melt-processing the polyvinylchloride composition of claim
 1. 24. The article of claim 23, whereinsaid melt processing involves calendering, injection molding orextrusion.
 25. The article of claim 23, wherein said polyvinyl chlorideresin is rigid.
 26. The article of claim 23, wherein said articlecomprises films, sheets, profiles or injection molded parts.
 27. Amethod of producing a fiber reinforced polyvinyl chloride compositioncomprising: compounding fibrous materials with a miscible admixture ofat least one polyvinyl chloride resin and at least one copolyester whichcomprises: (a) a dicarboxylic acid component comprising: (i) about 50 toabout 100 mole % of terephthalic acid residues; (ii) about 0 to about 50mole % of aromatic and/or aliphatic dicarboxylic acid residues having upto 20 carbon atoms; and (b) a glycol component comprising: (i) about 60to about 100 mole % of a modifying glycol consisting of 2 to 20 carbonatoms; and (ii) about 0 to about 40 mole % of a second modifying glycolconsisting of 2 to 20 carbon atoms; wherein the total mole % of thedicarboxylic acid component is 100 mole %, and wherein the total mole %of the glycol component is 100 mole %; to produce a viscousthermoplastic material; extruding the compound through a die to producepellets; and introducing the pellets into a calendering, extrusion orinjection molding process to produce fiber reinforced polyvinyl chloridearticles, wherein the copolyester is amorphous and has a T_(g) of about90° C. or higher.
 28. A method of producing a fiber reinforced polyvinylchloride composition comprising: compounding fibrous materials with atleast one copolyester which comprises: (a) a dicarboxylic acid componentcomprising: (i) about 50 to about 100 mole % of terephthalic acidresidues; (ii) about 0 to about 50 mole % of aromatic and/or aliphaticdicarboxylic acid residues having up to 20 carbon atoms; and (b) aglycol component comprising: (i) about 60 to about 100 mole % of amodifying glycol consisting of 2 to 20 carbon atoms; and (ii) about 0 toabout 40 mole % of a second modifying glycol consisting of 2 to 20carbon atoms; wherein the total mole % of the dicarboxylic acidcomponent is 100 mole %, and wherein the total mole % of the glycolcomponent is 100 mole %; to produce a viscous thermoplastic material;mixing the compounded composition with a polyvinyl chloride resin tocreate a polyvinyl chloride composition of about 1 to about 65 percentfibrous materials content based on the total weight of the composition;extruding the polyvinyl chloride composition through a die to producepellets; and introducing the pellets into a calendering, extrusion orinjection molding process to produce fiber reinforced polyvinyl chloridearticles, wherein the copolyester is amorphous and has a T_(g) of about90° C. or higher.
 29. The method of claim 27 or 28, wherein thecopolyester has a viscosity range of about 1,000 poise to about1,000,000 poise measured at a temperature of about 170° C. to about 230°C. and a shear rate of 10 s⁻¹, and a surface energy of equal to orgreater than about 40 dynes per cm and wherein the content of thefibrous materials is up to about 65% by weight based on the total weightof the composition.
 30. The method of claim 27 or 28, wherein thecopolyester has a viscosity range of about 1,000 poise to about1,000,000 poise measured at a temperature of about 170° C. to about 230°C. and a shear rate of 10 s⁻¹, and a surface energy of equal to orgreater than about 40 dynes per cm and wherein the content of thefibrous materials is at least about 30% by weight based on the totalweight of the composition.
 31. The method of claim 27 or 28, whereinsaid polyvinyl chloride composition is rigid.
 32. The method of claim 27or 28, wherein the fibrous materials are glass fibers.
 33. The method ofclaim 27 or 28, wherein the fibrous materials are fiberglass, glassfibers, carbon fibers, boron fibers, whisker, metallic fibers, inorganicfibers, aramid fibers, basalt fibers, mineral fibers, or combinationsthereof.
 34. A polyvinyl chloride article made using the method of claim27 or 28 having a Tg up to 110° C. or a HDT of up to 130° C.
 35. Themethod of claim 27 or 28, wherein the articles are articles of buildingand construction, corner profiles, decking, fencing, railings, soffits,vinyl siding, cladding, window profiles, door frames, siding, fences,gutters, pipes, piping, electrical and electronic enclosures, electricaljunction boxes, automobile interiors and exteriors, appliances, officeequipment, sign enclosures, medical devices, aircraft interiors, orother high temperature applications.
 36. An article of manufacturecomprising the polyvinyl chloride compositions of claim
 1. 37. Themethod of claim 27 or 28, wherein said polyvinyl chloride resin is apolyvinyl chloride resin, chlorinated polyvinyl chloride resin, oralloys thereof.
 38. The method of claim 27 or 28, wherein saidcomposition further comprising at least one additive selected from thegroup consisting of processing aids, plasticizers, stabilizers, impactmodifiers, biocides, flame retardants, foaming agents, blowing agents,thermal stabilizers, UV stabilizers, UV absorbers, minerals, pigments,dyes, colorants, fillers, fibers, waxes, fusion promoters, antioxidants,antistatic agents, release agents, lubricants, additional resins, andheat distortion temperature modifiers.